CN1192094C - Solid detergent compositions - Google Patents

Abstract

The present invention relates to a solid detergent composition comprising an aluminosilicate builder and an anionic surfactant and comprising n components (i), n being at least 2, wherein the aluminosilicate builder is present in all said groups The content in the composition is at least 5% by weight of the composition, and the content of anionic surfactant in all said components is at least 5% by weight of the composition, and the content of anionic surfactant and aluminosilicate builder The degree of mixing (M) is 0-0.7, M as defined in the specification.

Description

solid detergent composition

field of invention

The present invention relates to solid compositions comprising two or more components comprising aluminosilicate builders and surfactants which provide improved wash performance, improved release to the wash liquor and reduced residue on fabrics form.

Background of the invention

All detergents on the market contain surfactants and builders. One of the most commonly used detergents in phosphorus-free detergents is aluminosilicate. They are inexpensive builders and have the added advantage of being easy to manufacture. They are in fact useful processing aids as they are very good stylists, builders or carrier materials for other detergent ingredients. Thus, most detergents contain a base powder which is prepared by spray drying a slurry of aluminosilicate and surfactant or by agglomerating aluminosilicate and surfactant. Also, aluminosilicates can be used as dedusting agents to reduce stickiness or caking of the product.

A problem encountered with these detergents containing builder systems including aluminosilicates is that they tend to cause fabric residue. These residues contain detergent products that are encased in fabrics and/or are insoluble in water. Consumers can clearly see these spots on the fabric.

Another problem encountered with detergents, especially solid detergents, is that they tend to gel when in contact with water. This leads to poor dispersibility of the product from the feed drawer or dosing device and also to poor solubility of the product in the wash water. This leaves residues in drawers, feeders, washing machines and on fabrics where these spots can be clearly seen. Surfactants in particular have been found to gel when in contact with water.

The present inventors have now surprisingly found that these problems are particularly pronounced when the surfactant and the aluminosilicate are in intimate contact with each other in the detergent, for example when they are intimately mixed in the detergent. This is the case, for example, in most known and commonly used base powders containing agglomerated or spray-dried powders. The inventors have now found that when almost all anionic surfactants and aluminosilicates are intimately mixed with one another, not only mainly residue formation problems but also gelling problems or dissolution or dispersion problems arise in most known products. They found that these problems were reduced or even completely resolved when the degree of intimate mixing was reduced or even completely avoided.

Therefore, the present inventors have found that the aluminosilicate and the surfactant are still added to the solution of the detergent, but in a different way: the present invention thus provides the ability to combine at least two components in such a way that a limited degree of intimate mixing results. A detergent comprising surfactants and aluminosilicates.

The detergents of the present invention reduce fabric residue, especially insoluble detergent ingredients, reduce gelling, and improve dispersion and solubility. It has been found that these advantages are obtained by any conventional means of adding detergent to the wash liquor, including: using a dosing drawer, a dosing device, or adding detergent to the wash liquor before adding the laundry or adding washing on top of the laundry. agent.

The composition may contain a foaming system to further aid in dispersion or dissolution or foaming.

Brief description of the invention

The present invention provides a detergent composition comprising an aluminosilicate builder and an anionic surfactant and comprising n components (i), n being at least 2, wherein the aluminosilicate builder is present in all The components are present in an amount of at least 5% by weight of the composition, and the anionic surfactant is present in all of the components in an amount of at least 5% by weight of the composition, whereby the anionic surfactant and the aluminosilicate The mixing degree (M) of the builder is 0-0.7, and M is

∑ ⁿ _i＝1 √(σ ₁ ·ζ _i )

σ is the fraction of anionic surfactant of the composition contained in component (i); ζ is the fraction of aluminosilicate of the composition contained in component (i).

The composition is in particular in the form of granules, extrudates, pellets or lozenges, or in the form of tablets.

The present invention also relates to the use of a detergent composition or a mixture thereof comprising at least two components of an aluminosilicate and an anionic surfactant, wherein the aluminosilicate represents at least 5% by weight of the composition and the anionic surfactant At least 5% by weight of the composition, the anionic surfactant and aluminosilicate builder have a degree of mixing (M) of 0 to 0.7, M as defined above, in order to enhance the release of the detergent into the wash water.

The release of the detergent composition into the wash water is improved. For the purposes of the present invention, this means that the composition reduces fabric residue, especially water-insoluble detergent ingredients such as aluminosilicates, improves the dispersibility of the detergent composition, increases the solubility of the detergent, Detergent gelling and/or detergent clump formation on fabrics is reduced and the risk of fabric damage for bleach-containing compositions is reduced.

Detailed description of the invention

The detergent compositions herein contain at least two components including anionic surfactants or aluminosilicates or mixtures thereof, for which purpose a mixture of aluminosilicates and surfactants is present as one or more components , the degree of mixing M as defined above is lower than 0.7. Thus, each component contains part or all of the aluminosilicate, all or part of the anionic surfactant or a mixture thereof, provided that M is 0-0.7.

The components of the detergent compositions of the present invention each contain at least two ingredients, including anionic surfactants and/or aluminosilicates, which are intimately admixed. For the purposes of the present invention, this means that two or more ingredients in a component are distributed substantially evenly in the component.

Preferably, a component is such that when it contains anionic surfactants, the content of anionic surfactants is less than 95% by weight of the component, preferably less than 85% or even less than 80%, whereby anionic surfactants can be preferred The surfactant is present in an amount of at least 5%, preferably at least 10%, more preferably at least 20%, or even at least 30%, or even 35%, by weight of the component.

Preferably, a component is such that when it contains aluminosilicate, the aluminosilicate content is less than 95%, preferably less than 85%, or even less than 80% by weight of the component, whereby aluminum may be preferred The silicate content is at least 5%, preferably at least 10%, by weight of the component.

It should be understood that the detergent compositions herein may also contain other intimate mixtures of anionic surfactants and aluminosilicates. Likewise, the detergent compositions may contain other ingredients which are not in intimate admixture with one another and thus not included in the components of the composition as defined herein. For example, the compositions may contain detergent ingredients that are sprayed on or dry added to the components herein.

Said components together contain aluminosilicate builder at a minimum level of 5% by weight of the composition and anionic surfactant at a level of at least 5% by weight of the composition. Preferably, the components contain aluminosilicate in an amount of at least 7%, or more preferably at least 10% or even 15%, by weight of the composition. Depending on the precise formulation of the composition and the conditions of use, the compositions of the invention may contain even higher levels of aluminosilicate, eg greater than 20% or even greater than 25%, while still having improved release of detergent into the wash liquor.

Preferably at least 7% or more preferably at least 10% or even at least 12% of anionic surfactant is present in the composition by weight of the composition. Depending on the precise formulation of the composition and the conditions of use, it may be preferred that the anionic surfactant is present in an amount of 18% or more by weight of the composition.

It may be preferred that detergent compositions contain other dry-added aluminosilicates, especially to remove dust from detergent ingredients, thereby reducing the risk of caking and/or to impart a whitening effect to the product.

Preferably, M is lower than 0.65, or even lower than 0.45 or even 0.4 or even 0.35, it may be preferred that M is zero. One aspect of the present invention is that M is 0-0.5. There are therefore no other ingredients in detergent compositions containing aluminosilicates and anionic surfactants. Whether this is preferred, for example, will depend on the level of aluminosilicate and anionic surfactant in the detergent, the presence of other ingredients in the formulation and the amount of components in the formulation.

The components herein are preferably granules having a particle size of at least 50 microns, preferably said granules have a weight average particle size greater than 150 or greater than 250 microns or even greater than 350 microns, as determined by sieving on sieves of different mesh sizes. The composition is determined by calculating the portion remaining on the sieve and the portion passing through the sieve.

It may be preferred that at least one component is prepared by spray drying methods known in the art and at least one component is prepared by agglomeration methods known in the art.

Preferably, the components have a density from 250 g/l to 1500 g/l, more preferably at least one component, preferably all components have a density from 400 g/l to 1200 g/l, more preferably 500 g/l to 900 g/l .

A highly preferred further ingredient in the detergent compositions herein may be an oxygen-based bleach, preferably comprising a source of hydrogen peroxide, preferably perhydrate and a bleach activator as described hereinafter. The improved release of the product into the wash liquor has been found to result in enhanced release of the bleaching systems herein which reduces the risk of bleach deposition on fabrics and risk of fabric damage on contact.

Another preferred additional ingredient is one or more other builders, for example one or more of the monomeric, oligomeric or polycarboxylate builders and/or crystalline layered silicates described hereinafter Builder material.

Also, depending on the use and the particular formulation of the composition, detergent compositions may be substantially free of nonionic alkoxylated alcohol surfactants, which have been found to cause gelling or dispersion or dissolution problems, to be sprayed on specifically. It may then be preferred that the composition contains other nonionic surfactants, preferably nonionic surfactants which are solid at room temperature. A further advantage may be that the elimination of the nonionic alkoxylated alcohol sprayed on reduces or eliminates the powdery material such as fine aluminosilicate normally required to remove detergent granules incorporating these liquid nonionic surfactants. Not only does this reduce processing complexity, but it also reduces the degree of mixing or contacting of surfactants.

Furthermore, the inventors have discovered that in some embodiments of the present invention, the presence of a flocculating polymer and a polycarboxylate polymer such as those described herein can advantageously reduce aluminosilicate and one or more organic polymeric compounds. The mixing degree of the substance. The degree of mixing of aluminosilicate and one or more of these polymers can be determined by the above formula, where σ refers to the weight fraction of a particular polymer in a component. This has been found to reduce the formation of fabric residue on the fabric, especially of water insoluble components such as aluminosilicates.

In some embodiments of the present invention, when amorphous silicate is present, it may also be advantageous to reduce the degree of mixing between amorphous silicate and anionic surfactant, especially in the presence of anionic surfactant to be spray dried. In mixtures, the amount of silicate present may advantageously be reduced, for example to a content below 3%, or even below 2%, or even below 1% or even 0%, by weight of the mixture.

Aluminosilicate

Suitable aluminosilicates herein are zeolites having the unit cell formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ]·xH ₂ O, wherein z and y are at least 6; the molar ratio of z to y is 1.0 -0.5, x is at least 5, preferably 7.5-276, more preferably 10-264. The aluminosilicate is preferably in hydrated form, and preferably crystalline, containing 10-28%, more preferably 18-22% water in bound form. However, overdried aluminosilicates can advantageously be added.

The aluminosilicates may be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available identified as Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O

where x is 20-30, especially 27. Zeolite X has the formula:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]·276H ₂ O

anionic surfactant

Any anionic surfactant may be added to the compositions of the present invention. The anionic surfactants herein preferably contain at least one sulfate surfactant and/or one sulfonate surfactant or mixtures thereof. It may be preferred that the anionic surfactants contain alkyl sulfonate surfactants alone or optionally in combination with fatty acids or soap salts thereof. Alternatively, it may be preferred that the composition contains only alkyl sulphate surfactants, but thus it is preferred that at least one mid-chain branched alkyl surfactant is present or at least two alkyl surfactants are present.

Depending on the precise formulation of the composition and its use, it may be preferred that the compositions herein contain a particulate component as described above, preferably in the form of flakes of an alkyl sulfate or sulfonate surfactant, preferably an alkyl benzene sulfonate, It is present at a concentration of 85-95% of the granules or flakes, which are mixed with other detergent components or ingredients, with the remainder being sulphate and moisture.

Other possible anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty amides of methyl taurate, alkyl succinates and sulfosuccinates, sulfosuccinic acid monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants according to the present invention include C ₅ -C ₂₀ linear or branched chain alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids and any mixtures thereof.

Highly preferred are C ₁₂ -C ₁₆ linear alkylbenzene sulfonates. Preferred salts are sodium and potassium salts.

The alkyl ester sulfonated surfactants are also suitable for the present invention, preferably these are of the formula:

R ¹ -CH(SO ₃ M)-(A) _x -C(O)-OR ²

Wherein R ¹ is a C ₆ -C ₂₂ hydrocarbon group, R ² is a C ₁ -C ₆ alkyl group, A is a C ₆ -C ₂₂ alkylene group, an alkenylene group, x is 0 or 1, and M is a cation. The counter ion M is preferably sodium, potassium or ammonium.

The alkyl ester sulfonated surfactant is preferably an alpha-sulfoalkyl ester of the above formula where x is zero. Preferably R ¹ is an alkyl or alkenyl group of 10-22, preferably 16 carbon atoms, and x is preferably 0. ^R2 is preferably ethyl or more preferably methyl.

It may be preferred that ^R1 in the ester is derived from an unsaturated fatty acid, preferably with 1, 2 or 3 double bonds. It may also be preferred that ^R1 in the ester is derived from a naturally occurring fatty acid, preferably palmitic acid or stearic acid or mixtures thereof.

Anionic Alkyl Sulfate Surfactant

Anionic sulfate surfactants herein include linear or branched primary and secondary alkyl sulfates and pyrosulfates, alkyl ethoxy sulfates with an average ethoxylation number of 3 or less, fatty oleoyl Glyceryl Sulfate, Alkylphenol Oxyethylene Ether Sulfate, C ₅ -C ₁₇ Acyl-N-(C ₁ -C ₄ Alkyl) and -N-(C ₁ -C ₂ Hydroxyalkyl) Glucosamine Sulfate and sulfates of alkyl polysaccharides.

The primary alkyl sulfate surfactants are preferably selected from linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably C ₁₁ -C ₁₅ linear or branched chain alkyl sulfates, or more preferably C ₁₂ - _C14 linear alkyl sulfate.

Preferred secondary alkyl sulfate surfactants are of the formula:

R ³ -CH(SO ₄ M)-R ⁴

Wherein R ³ is a C ₈ -C ₂₀ cycloalkyl (hydrocycarbyl), R ⁴ is a cycloalkyl, and M is a cation.

The alkyl ethoxy sulfate surfactants are preferably selected from C ₁₀ -C ₁₈ alkyl sulfates that have been ethoxylated with 0.5-3 moles of ethylene oxide per unit molecule. More preferably, the alkyl ethoxy sulfate surfactant is C ₁₁ -C ₁₈ , most preferably C ₁₁ - C ₁₅ Alkyl Sulfate.

A particularly preferred aspect of the invention is the use of mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Preferred salts are sodium and potassium salts.

Medium Chain Branched Anionic Surfactant

Preferred mid-chain branched primary alkyl sulfate surfactants for use herein are of the formula:

These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain including the sulfated carbon atoms), which preferably consists of 12-19 carbon atoms, with branched primary alkyl moieties It preferably contains a total of at least 14 and preferably not more than 20 carbon atoms. In surfactant systems containing more than one of these sulfate surfactants, the average total number of carbon atoms in the branched primary alkyl moiety preferably ranges from greater than 14.5 to about 17.5. Accordingly, the surfactant system preferably contains at least one branched primary alkyl sulfate surfactant compound wherein the longest linear carbon chain is not less than 12 carbon atoms or not more than 19 carbon atoms and includes branched chains. The total number of carbon atoms must be at least 14, further the average total number of carbon atoms in the branched primary alkyl moiety is in the range of greater than 14.5 to about 17.5.

R, R ¹ and R ² are each selected from H and C ₁ -C ₃ alkyl (preferably H or C ₁ -C ₂ alkyl, more preferably H or methyl, most preferably methyl), as long as R, R ¹ and ^R2 are not H at the same time. Also, when z is 1 at least R or ^R1 is not H.

Depending on the synthesis method, M is H or a salt-forming cation. w is an integer of 0-13; x is an integer of 0-13; y is an integer of 0-13; z is an integer of at least 1; and w+x+y+z is an integer of 8-14.

Preferably, the mid-chain branched primary alkyl sulfate surfactant is a primary alkyl sulfate surfactant having a total carbon number of 16, wherein the main chain has 13 carbon atoms, and has 1, 2 or 3 branches Units (i.e. R, ^R1 and/or ^R2 ) with a total of 3 carbon atoms, (thereby a total of at least 16 carbon atoms), the preferred branching unit may be one propyl branching unit or three methyl chain unit.

Another preferred surfactant is branched primary alkyl sulfates having the formula:

wherein the total number of carbon atoms including branching is from 15 to 18, and when more than one of these sulfates are present, the average total number of carbon atoms in the branched primary alkyl portion having the above formula is in the range of greater than 14.5 to about 17.5; R ¹ and R ² are each independently H or C ₁ -C ₃ alkyl; M is a water-soluble cation; x is 0-11; y is 0-11; z is at least 2; 13; as long as R ¹ and R ² are not both H.

double anionic surfactant

The dianionic surfactants are also useful anionic surfactants in the present invention, especially those of the formula:

wherein R is an optionally substituted chain length of C ₁ -C ₂₈ , preferably C ₃ -C ₂₄ , most preferably C ₈ -C ₂₀ alkyl, alkenyl, aryl, alkaryl, ether, ester group, amino group or amido group, or H; A and B are respectively selected from chain lengths of C ₁ -C ₂₈ , preferably C ₁ -C ₅ , most preferably C ₁ -C ₂ alkylene, alkenylene, (poly ) alkyleneoxy, hydroxyalkylene, arylalkylene or amidoalkylene, or a covalent bond, and preferably A and B together contain at least 2 atoms; A, B and R together contain 4 to about 31 carbon atoms; X and Y are anionic groups selected from carboxylate, preferably sulfate and sulfonate, z is 0 or preferably 1; and M is a cationic moiety, preferably substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ions.

The most preferred dianionic surfactants have the above formula, wherein R is an alkyl group having a chain length of C ₁₀ -C ₁₈ , A and B are respectively C ₁ or C ₂ , X and Y are both sulfate, and M is potassium , ammonium or sodium ions.

Preferred dianionic surfactants herein include:

(a) 3 pyrosulfate compounds, preferably 1,3 C7-C23 (i.e., the total number of carbon atoms in the molecule) linear or branched chain alkyl or alkenyl disulfates, more preferably having the formula:

wherein R is a straight or branched chain alkyl or alkenyl with a chain length of about _C4 to about _C20 ;

(b) 1,4 pyrosulfate compounds, preferably 1,4 C8-C22 straight or branched chain alkyl or alkenyl pyrosulfates, more preferably having the following formula:

wherein R is a linear or branched chain alkyl or alkenyl group with a chain length of about _C4 to about _C18 ; preferably R is selected from the group consisting of octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl Alkyl, octadecyl, and mixtures thereof; and

(c) 1,5 pyrosulfate compounds, preferably 1,5 C9-C23 linear or branched chain alkyl or alkenyl pyrosulfates, more preferably having the following formula:

wherein R is a linear or branched alkyl or alkenyl group with a chain length of about C ₄ to about C ₁₈ .

It may be preferred that the dianionic surfactants of the present invention are alkoxylated dianionic surfactants.

The alkoxylated dianionic surfactants of the present invention comprise a framework of at least 5 carbon atoms to which are attached two anionic substituents separated by at least 3 atoms. At least one of said anionic substituents is an alkoxy linked sulfate or sulfonate. The framework may include, for example, any group selected from the group consisting of alkyl, substituted alkyl, alkenyl, aryl, ether, ester, amino and amido. Preferred alkoxy moieties are ethoxy, propoxy and combinations thereof.

The framework preferably comprises 5-32, preferably 7-28, most preferably 12-24 atoms. Preferably the framework comprises only carbon-containing groups, more preferably only hydrocarbyl groups. Most preferably the framework comprises only straight or branched chain alkyl groups.

The framework is preferably branched. Preferably at least 10% by weight of the backbone is branched, and the branches are preferably 1-5, more preferably 1-3, most preferably 1-2 atoms long (excluding sulfate or Sulfonate).

Preferred alkoxylated dianionic surfactants have the formula:

wherein R is an optionally substituted chain length of C ₁ -C ₂₈ , preferably C ₃ -C ₂₄ , most preferably C ₈ -C ₂₀ alkyl, alkenyl, aryl, alkaryl, ether, ester A group, amino or amido group, or H; A and B are respectively selected from optionally substituted alkyl and alkenyl groups with a chain length of C ₁ -C ₂₈ , preferably C ₁ -C ₅ , most preferably C ₁ -C ₂ , or a covalent bond; EO/PO is an alkoxy moiety selected from ethoxy, propoxy, and mixed ethoxy/propoxy, where n and m are each from about 0 to about 10, at least m or n at least 1; A and B together contain at least 2 atoms; A, B and R together contain 4 to about 31 carbon atoms; X and Y are anionic groups selected from sulfate and sulfonate, provided at least one of X or Y is sulfate; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ion.

The most preferred alkoxylated dianionic surfactant has the above chemical formula, wherein R is an alkyl group with a chain length of C ₁₀ -C ₁₈ , A and B are respectively C ₁ or C ₂ , n and m are both 1, Both X and Y are sulfate, and M is potassium, ammonium or sodium ion.

Preferred alkoxylated dianionic surfactants herein include:

Ethoxylated and/or propoxylated pyrosulfate compounds, preferably C10-C24 linear or branched chain alkyl or alkenyl ethoxylated and/or propoxylated pyrosulfates, more preferably having Mode:

和

and

wherein R is a linear or branched alkyl or alkenyl group with a chain length of about _C6 to about _C18 ; EO/PO is an alkoxy moiety selected from the group consisting of ethoxy, propoxy and mixed ethoxy/propoxy and n and m are each from about 0 to about 10 (preferably from about 0 to about 5), wherein at least m or n is 1.

Anionic Carboxylate Surfactants

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ('alkyl carboxyl'), especially as described herein Certain secondary soaps.

Suitable alkyl ethoxy carboxylates include those having _the formula RO( _CH2CH2O ) _xCH2COO ^- M ⁺ , _wherein R is _C6 - _C18 alkyl, x is 0-10, and The distribution of the ethoxy groups is such that x is less than 20% by weight of the mass and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ₁ -CHR ₂ -O)-R ₃ wherein R is C ₆ -C ₁₈ alkyl and x is 1- 25, R _{and R} are selected from H, formic acid residues, succinic acid residues, hydroxysuccinic acid residues and mixtures thereof, R _is selected from H, substituted or unsubstituted hydrocarbons with 1-8 carbon atoms, and its mixture.

Suitable soap surfactants include secondary soap surfactants, containing a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are water soluble members selected from 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2 - Water-soluble salts of butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is a C ₅ -C ₁₇ linear or branched chain alkyl or alkenyl group, and R ¹ is a C ₁ -C ₄ alkyl group, and M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the sodium salt form.

foaming system

Any foaming system known in the art may be used in the compositions of the present invention. Preferred foaming systems include an acid source capable of reacting with an alkali source in the presence of water to produce gas.

The acid source is preferably present in an amount of from 0.5% to 35% by weight of the composition, more preferably from 1.0% or even 2% to 20% or even 4% to 20%.

It may be preferred that the acid source or part thereof and the alkali source or part thereof be contained in intimate admixture, for example in the form of compacted granules. The molar ratio of acid source to alkali source is preferably 50:1-1:50, more preferably 20:1-1:20, more preferably 10:1-1:10, whereby when an intimate mixture of acid source and alkali source is present When , the ratio is more preferably 5:1-1:3, more preferably 3:1-1:2, more preferably 2:1-1:2.

The acid source component may be any organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. Preferred acid source components include organic acids.

The acid compound is preferably substantially anhydrous or non-hygroscopic, and the acid is preferably water soluble. It may be preferred to overdry the acid source.

Suitable acid source components include citric acid, malic acid, maleic acid, fumaric acid, aspartic acid, glutaric acid, tartaric acid, succinic acid or adipic acid, sodium dihydrogen phosphate, boric acid or derivatives thereof. Particular preference is given to citric acid, maleic acid or malic acid.

Most preferably, the acid source is an acid compound having an average particle size of about 75-1180 microns, more preferably 150 microns to about 710 microns, obtained by sieving the acid source over a series of Tyler sieves. Sample calculated.

As discussed above, the foaming system preferably contains a source of alkalinity, however, for the purposes of the present invention it is understood that the source of alkalinity may be part of the foaming particles, or may be part of the cleanser containing the particles, Alternatively it may be present in the wash liquor, whereby the particles or the cleaning agent are added.

Any source of alkali capable of reacting with the acid source to produce a gas may be present in the particle, and may be any gas known in the art, including nitrogen, oxygen and carbon dioxide gas. Preferred may be perhydrate bleaches, including perborate and silicate materials. The source of alkalinity is preferably substantially anhydrous or non-hygroscopic. It may be preferred to overdry the alkali source.

Preferably the gas is carbon dioxide, thus the alkali source is preferably a carbonate source, which can be any carbonate source known in the art, and in a preferred embodiment, the carbonate source is a carbonate . Examples of preferred carbonates are alkaline earth and alkali metal carbonates, including sodium or potassium carbonate, sodium or potassium bicarbonate and sodium or potassium sesquicarbonate and any mixture thereof with ultrafine calcium carbonate, as in 1973 It is disclosed in German patent application 2321001 published on November 15th. Alkali metal percarbonates are also suitable sources of carbonates, which may be present together with one or more other carbonate sources.

The carbonates and bicarbonates preferably have an amorphous structure. The carbonates and/or bicarbonates can be coated with a coating material. It may be preferred that the particles of carbonates and bicarbonates have an average particle size of 75 microns or preferably 150 microns or greater, more preferably 250 microns or greater, preferably 500 microns or greater. It may be preferred that less than 20% by weight of the carbonates have a particle size of less than 500 microns as calculated by sieving a carbonate or bicarbonate sample over a series of Taylor sieves. Additionally or in addition to the preceding carbonates, it may be preferred that less than 60% or even 25% of the particles have a particle size below 150 microns, while less than 5% of the particles have a particle size greater than 1.18 mm, more preferably low Less than 20% of the particles had a particle size greater than 212 microns, calculated by sieving the carbonate or bicarbonate sample over a series of Taylor sieves.

other components

The compositions herein may contain other detergent ingredients. The precise nature of these other ingredients and the amounts added will depend upon the physical form of the composition containing the builder component and the precise nature of the laundering operation to be used.

Other ingredients include other builders, other surfactants, bleaches, enzymes, suds suppressors, lime soaps, dispersants, soil suspending and antiredeposition agents, soil release agents, perfumes, brighteners, photobleaching agents and other corrosion inhibitors.

Water-soluble or partially water-soluble builders

The compositions preferably contain one or more water-soluble or partially water-soluble builders.

These include crystalline layered silicates, organic carboxylates or carboxylic acids. Preferred crystalline layered silicates herein have the general formula:

NaMSi _x O _2x+1 ·yH ₂ O

Wherein M is sodium or H, x is 1.9-4, and y is 0-20. Such crystalline layered sodium silicates are described in EP-A-0164514 and processes for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the general formula above is 2, 3 or 4, and is preferably 2. M is preferably H, K or Na or a mixture thereof, preferably Na. Most preferred is α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ or δ-Na ₂ Si ₂ O ₅ , or mixtures thereof, preferably at least 75%-Na ₂ Si ₂ O ₅ , for example available from Clariant was obtained as NaSKS-6.

Said crystalline layered silicates, in particular of formula _{Na2Si2O5 ,} may optionally contain other elements like B, P, S, obtained for example by _the method described in EP578986-B.

The crystalline layered silicate may be in intimate admixture with other materials including one or more surfactants in the surfactant system herein. Preferred other materials are other water soluble builders including (poly)carboxylic acids and their salts such as acrylic acid and/or maleic acid polymers, mineral acids or salts including carbonates and sulfates, or small amounts of Other silicates include the amorphous silicates, metasilicates and aluminosilicates described herein.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or acid forms thereof, homo- or co-polymeric polycarboxylic acids or salts thereof, and mixtures of any of the foregoing, wherein the polycarboxylic acid comprises at least two carboxylic acids residues, which are separated from each other by not more than two carbon atoms.

The carboxylate or polycarboxylate builder can be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for cost and performance. In addition to these water-soluble builders, polymeric polycarboxylates, including homopolymers and copolymers of maleic and acrylic acid and their salts, can be present.

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxyl groups include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diethylene glycol ether, tartaric acid, hydroxymalonic acid and fumaric acid, and ether carboxylates acid salts and sulfinyl carboxylates.

Polycarboxylates containing three carboxy groups include, inter alia, the water-soluble citrates, aconitrates and citraconicates and succinate derivatives such as carboxymethoxysuccinate as described in British Patent 1379241 , lactyloxysuccinates described in British Patent 1389732 and aminosuccinates described in Dutch Application 7205873, and oxypolycarboxylates such as 2-oxa as described in British Patent 1387447 - 1,1,3-Propane tricarboxylates.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane as disclosed in British Patent 1,261,829 Tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patents 1,398,421 and 1,398,422 and US Patent 3,936,448 and the sulfonated pyrolyzed citrates described in British Patent 1,439,000. Preferred polycarboxylates are hydroxycarboxylates, especially citrates, containing up to three carboxy groups per molecule.

Most preferred may be citric, malic and fumaric acids, or salts or mixtures thereof.

Mixtures of the parent acids of monomeric or oligomeric polycarboxylate chelating agents or their salts, such as citric acid or citrate/citric acid mixtures, are also useful builder components.

Alkoxylated Nonionic Surfactants

Essentially any alkoxylated nonionic surfactant is suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants may be selected from the following classes: nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated Condensation products of oxylates/propoxylates with propylene glycol, and condensation products of nonionic ethoxylates with propylene oxide/ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactants

The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are suitable for use here. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particular preference is given to condensation products of alkyl alcohols containing 8 to 20 carbon atoms per mole with 2 to 10 moles of ethylene oxide.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the formula R ² CONR ¹ Z, wherein: R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, Propoxy or mixtures thereof, ethylene C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl); and R ₂ is C ₅ -C ₃₁ hydrocarbyl, preferably straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl group having a linear hydrocarbon chain with at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those of the formula: R ⁶ CON(R ⁷ ) ₂ wherein R ⁶ is an alkyl group containing 7-21, preferably 9-17 carbon atoms, and each R ⁷ is selected from H , C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and -(C ₂ H ₄ O) _x H, wherein x is 1-3.

Nonionic Alkyl Polysaccharide Surfactant

Alkylpolysaccharides suitable for use herein are disclosed in U.S. Patent 4,565,647, issued January 21, 1986 to Llenado, having a hydrophobic group containing 6-30 carbon atoms and a hydrophilic group containing 1.3-10 sugar units Agglomerated polysaccharides, such as polyglycosides.

Preferred alkylpolysaccharides have the formula:

R ² O(C _n H _2n O)t(glycosyl) _x

Wherein ^R is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains 10-18 carbon atoms, n is 2 or 3; t is 0-10, x 1.3-8. The glycosyl is preferably derived from glucose.

amphoteric surfactant

Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable amine oxides include those having the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ , wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, acylaminopropyl and alkylbenzene groups containing 8 to 26 carbon atoms or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixture thereof; x is 0-5, preferably 0-3; each R ⁵ is a group containing 1-3 A hydroxyalkyl group of carbon atoms or a polyoxyethylene group containing 1-3 oxyethylene groups. Preferred are C ₁₀ -C ₁₈ alkyl dimethylamine oxides and C ₁₀ -C ₁₈ amidoalkyl dimethylamine oxides.

A suitable example of an alkyl amphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use in the present invention.

Suitable betaines are those compounds having the formula R(R') ₂ N ⁺ R ^{2 COO-} , wherein R is C ₆ -C ₁₈ hydrocarbyl, each R ¹ is typically C ₁ -C ₃ alkyl, and R ² is a C ₁ -C ₅ hydrocarbon group. Preferred betaines are C ₁₂ -C ₁₈ dimethylcaproate and C _10-18 amidopropyl (or ethyl) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use in the present invention.

cationic surfactant

Cationic surfactants suitable for use in the detergents of the present invention include quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactant, wherein the remaining N positions are replaced by methyl, hydroxyethyl or hydroxypropyl replace. Monoalkoxylated and dialkoxylated amine surfactants are also preferred.

Another suitable group of cationic surfactants which may be used in the detergent compositions or components thereof of the present invention are cationic ester surfactants. The cationic ester surfactant is a preferably water-dispersible, surfactant-capable compound comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

Suitable cationic ester surfactants include choline ester surfactants as disclosed, for example, in US4228042, 4239660 and 4260529.

In a preferred aspect, the ester bond and the cationic charged group in the surfactant molecule are composed of at least 3 atoms (i.e. three atom chain length), preferably 3-8 atoms, more preferably 3-5 atoms, Most preferably the spacer groups consisting of chains of 3 atoms will separate each other. The atoms forming the chain of the spacer are selected from carbon, nitrogen and oxygen atoms and any mixtures thereof, provided that any nitrogen or oxygen atom in the chain is bonded only to carbon atoms in the chain. Thus, spacer groups do not include, for example, -OO- (ie, peroxide), -NN-, and -NO- linkages, while spacer groups include, for example, _-CH2- O- _CH2- and _-CH2- NH- CH ₂ -bond. In a preferred aspect, the spacer chain comprises only carbon atoms, most preferably the chain is a hydrocarbon chain.

Cationic monoalkoxylated amine surfactants

Particularly preferred cationic monoalkoxylated amine surfactants of the general formula I are particularly preferred according to the invention:

wherein ^R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R ^and R are ^each independently An alkyl group containing 1 to about 3 carbon atoms, preferably methyl, most preferably ^R2 and ^R3 are both methyl; ^R4 is selected from H (preferred), methyl and ethyl; X- is to provide electrical neutrality Anions of, such as chloride, bromide, methylsulfate, sulfate, etc.; A is alkoxy, especially ethoxy, propoxy or butoxy; and p is 0 to about 30, preferably 2- About 15, most preferably 2 to about 8.

Preferred ^ApR4 groups in formula I have p = 1 and are hydroxyalkyl groups of not more than 6 carbon atoms, wherein the hydroxyl group is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Particularly preferred ApR ⁴ groups are -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH(CH ₃ )OH and -CH(CH ₃ )CH ₂ OH, of which -CH ₂ CH ₂ OH. Preferably the ^R1 group is a straight chain alkyl group. Straight-chain R ¹ groups having 8-14 carbon atoms are preferred.

Another highly preferred cationic monoalkoxylated amine surfactant for use herein is the formula:

wherein ^R is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any anion suitable to provide charge balance, preferably chloride or bromide .

It should be noted that compounds of the preceding type include the ethoxy (CH ₂ CH ₂ O) units (EO) replaced by butoxy, isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH Those replaced by (CH ₃ )O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

The level of cationic monoalkoxylated amine surfactants used in the detergent compositions herein is preferably from 0.1 to 20%, more preferably from 0.2 to 7%, most preferably from 0.3 to 3.0%, by weight of the composition.

Cationic dialkoxylated amine surfactants

The cationic dialkoxylated amine surfactants preferably have the general formula II:

wherein R ¹ is an alkyl or alkenyl moiety containing about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably about 10 to about 14 carbon atoms; R ² is an alkyl or alkenyl moiety containing 1 to 3 An alkyl group of carbon atoms, preferably a methyl group; each ^of R and ^R can vary and be selected from H (preferably), methyl and ethyl, and X ^- is an anion sufficient to provide electrical neutrality, such as chloride, bromide, Methylsulfate, Sulfate, etc. A and A' may each vary and are each selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O-), propoxy, butoxy and mixtures thereof; p is 1 to about 30, preferably 1 to about 4, and q is 1 to about 30, preferably 1 to about 4, most preferably both p and q are 1.

A highly preferred cationic dialkoxylated amine surfactant for use herein is the formula:

Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbon groups and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl groups and mixtures thereof. X is any anion suitable to provide charge balance, preferably ammonium. According to the general structure of cationic dialkoxylated amines above, since in a preferred compound ^R is derived from (coconut) C ₁₂ -C ₁₄ alkyl moiety fatty acid, ^R is methyl and ApR ^and A'qR ^are each monoethoxy.

Other cationic dialkoxylated amine surfactants useful herein include compounds of the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbon group, preferably C ₁₀ -C ₁₄ alkyl, independently p is 1 to about 3, q is 1 to about 3, R ² is C ₁ -C ₃ alkyl, preferably methyl , and X is an anion, especially chloride or bromide.

Other compounds of the preceding type include the ethoxy (CH ₂ CH ₂ O) unit (EO) replaced by butoxy (Bu) isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH(CH ₃ O] units (i-Pr) or n-propoxy units (Pr), or those replaced by mixtures of EO and/or Pr and/or i-Pr units.

perhydrate bleach

A highly preferred further ingredient in the compositions of the present invention is an oxygen bleach, preferably comprising a source of hydrogen peroxide and a bleach precursor or activator.

Preferred sources of hydrogen peroxide are perhydrate bleaches, such as metal perborates, more preferably metal percarbonates, especially the sodium salts thereof. Perborate may be mono- or tetrahydrated. Sodium percarbonate has a formula corresponding to _{2Na2CO3-3H2O2} and _is commercially available as _a crystalline _solid .

Particular preference is given to coating percarbonate. Suitable coating agents are known in the art and include silicates, magnesium salts and carbonates.

Potassium persulfate, sodium persulfate are other optional inorganic perhydrate salts for use in the detergent compositions herein.

Organic peroxyacid bleaching system

A preferred feature in the compositions of the present invention is an organic peroxyacid bleaching system. In a preferred embodiment the bleach system comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of organic peroxyacids is carried out by in situ reaction of said precursors with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleaches of the claimed invention. In another preferred embodiment, a preformed organic peroxyacid is added directly to the composition. It is also conceivable to mix a composition comprising a mixture of a hydrogen peroxide source and an organic peroxyacid precursor with a preformed organic peroxyacid.

Peroxyacid Bleach Precursors

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce peroxyacids. Typically peroxyacid bleach precursors can be shown as follows:

Wherein L is a leaving group, and X is almost any functional group, as long as the structure of the peroxyacid produced during perhydrolysis is as follows:

The peroxyacid bleach precursor compounds are preferably incorporated in an amount of from 0.5 to 20%, more preferably from 1 to 15%, most preferably from 1.5 to 10% by weight of the detergent composition.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, said precursors being selected from various classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials of these types are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

leaving group

The leaving group, hereinafter the L group, must be sufficient to react in the perhydrolysis reaction to proceed within an optimal time frame (eg wash cycle). However, if L is too reactive, the active will be difficult to use stably in bleaching compositions.

Preferably the L group is selected from the following groups:

和

and

和

and

and mixtures thereof, wherein R ¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R ³ is an alkyl group containing 1-8 carbon atoms, R ⁴ is H or R ³ , and Y is H or a solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substituted with almost any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amino, nitrosyl, amido, and ammonium or alkylammonium groups.

Preferred solubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ³ ) ₄ X ^- and O<--N(R ³ ) ₃ , most Preferred are -SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ , wherein R ³ is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that imparts solubility to the bleach activator, and X is a cation that imparts solubility to the bleach activator. Soluble anions. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl percarboxylic acid bleach precursor

Alkyl percarboxylic acid bleach precursors form percarboxylic acids by perhydrolysis. Preferably such precursors provide peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds include N,N,N ¹ ,N ¹ tetraacetylated alkylenediamines wherein the alkylene group contains 1 to 6 carbon atoms, especially the alkylene Compounds containing 1, 2 and 6 carbon atoms. Particular preference is given to tetraacetylethylenediamine (TAED). The TAED is preferably absent from the agglomerated particles of the present invention, but is preferably present in detergent compositions comprising said particles.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium Sulfonate (ABS) and Pentaacetyl Glucose.

Amide Substituted Alkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable for the present invention and include those of the general formula:

or

Wherein R ^is an alkyl group with 1-14 carbon atoms, R is ^an alkylene group with 1-14 carbon atoms, R is ^H or an alkyl group with 1-10 carbon atoms, and L can be almost any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Precursor of perbenzoic acid

Perbenzoic acid precursor compounds provide perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, and benzoylation products of sorbitol, glucose, and all sugars with benzoylating reagents , and imides include N-benzoyl succinimide, tetrabenzoyl ethylenediamine, and N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl-containing benzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine, and benzoylpyroglutamate.

preformed organic peroxyacids

Additionally or alternatively, the detergent compositions may typically contain organic peroxyacid bleach precursor compounds, pre-formed organic peroxyacids, in amounts of 1 to 15 wt%, more preferably 1 to 10 wt%, by weight of the composition.

A preferred class of organic peroxyacid compounds are amide substituted compounds of the general formula:

Wherein ^R is an alkyl, aryl or alkaryl group with 1-14 carbon atoms, ^R is an alkylene, arylene and alkarylene group with ^1-14 carbon atoms, and R is H or An alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid. Mono- and diperazelaic acid, mono- and dipertridecanedioic acid and N-phthaloylaminoperoxycaproic acid are also suitable for the present invention.

Heavy metal ion chelating agent

Heavy metal ion sequestrants are also additional ingredients useful in the present invention. By heavy metal ion sequestrant is meant a component of the invention that chelates heavy metal ions. These components may also have limited calcium and magnesium chelation capacity, but preferably they exhibit selectivity for binding heavy metal ions such as iron, manganese and copper. Builders are therefore not considered for the purposes of the present invention.

Heavy metal ion sequestrants are typically present at 0.005-10%, preferably 0.1-5%, more preferably 0.25-7.5%, most preferably 0.3-2%, by weight of the composition.

Heavy metal ion sequestrants suitable for use herein include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethyl 1-hydroxydiphosphonates, and nitrilotrimethylene Phosphonates.

Preference is given to diethylenetriaminepenta(methylenephosphonate), ethylenediaminetris(methylenephosphonate), 1,6-hexamethylenediaminetetrakis(methylenephosphonate) and hydroxymethylene Ethyl 1,1 bisphosphonate, 1,1 etidyl diphosphonic acid and 1,1 hydroxyethylene dimethylene phosphonic acid.

Other suitable heavy metal ion sequestrants for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine Disuccinic acid or any salt thereof.

Other suitable heavy metal ion sequestrants for use in the present invention are the iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid described in EP-A-317542 and EP-A-399133. Also suitable are the iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agents described in EP-A-516102 this invention. β-Alanine-N, N'-diacetic acid, Aspartic acid-N, N'-diacetic acid, Aspartic acid-N-monoacetic acid and iminodisuccinate described in EP-A-509382 Acid sequestrants are also suitable.

EP-A-476257 describes suitable amino chelating agents. EP-A-510331 describes suitable chelating agents from collagen, keratin or casein. EP-A-528859 describes suitable alkyliminodiacetic acid sequestrants. Also suitable are picolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Glycylamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS ) is also suitable.

Particular preference is given to diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS) and ethylenediphosphonic acid or their alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof .

enzyme

Another preferred ingredient for use in the present invention is one or more other enzymes.

Preferred other enzymes include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases commonly added to detergent compositions and peroxidase. Suitable enzymes are disclosed in US3519570 and US3533139.

organic polymer

Organic polymers are preferred additional components in the compositions of the present invention.

By organic polymer is meant herein almost any organic polymer commonly used as binder, dispersant and anti-redeposition and soil suspension agent in detergent compositions, including any of the clay flocculants described herein. High molecular weight organic polymers including quaternary ethoxylated (poly)amine clay removers/anti-redeposition agents.

Organic polymers are typically incorporated into the detergent compositions of the present invention at levels of 0.01-30%, preferably 0.1-15%, most preferably 0.5-10% by weight of the composition.

Examples of organic polymers include water-soluble organic homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acids include at least two carboxyl groups separated from each other by not more than 2 carbon atoms. Polymers of the latter type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates having a MWt of 1,000-5,000 and their copolymers with maleic anhydride, these polymers having a molecular weight of 2,000-100,000, especially 40,000-80,000.

Polyamino compounds useful in the present invention include those derived from aspartic acid, such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Tetrapolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5000-10000, are also suitable for the present invention.

Other organic polymers suitable for incorporation into the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other useful organic polymers are polyethylene glycols, especially those having a molecular weight of 1000-10000, more preferably 2000-8000 and most preferably about 4000.

Highly preferred polymeric components in the present invention are cotton and non-cotton soil release polymers such as Scheibel et al. US Patent 4,968,451 and Gosselink et al. US Patent 5,415,807, especially US Application 60/051517.

Another organic compound that is a preferred clay dispersant/anti-redeposition agent for use in the present invention may be an ethoxylated cationic monoamine and diamine of the formula:

Wherein X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0-20, preferably 0-4 (such as ethylene, ethylene Propyl, 1,6-hexylene), b is 1 or 0; for cationic monoamine (b=0), n is at least 16, typically 20-35; for cationic diamine (b=1) For example, n is at least about 12, typically from about 12 to about 42.

Other dispersants/anti-redeposition agents useful in the present invention are described in EP-B-011965 and US4659802 and US4664848.

Antifoam system

The detergent compositions of the present invention, when formulated for use in machine wash compositions, may contain a suds suppressor system in an amount of 0.01-15%, preferably 0.02-10%, most preferably 0.05-3%, by weight of the composition.

Suds suppressing systems suitable for use herein may comprise essentially any known antifoam compound including, for example, silicone antifoam compounds and 2-alkyl alcohol antifoam compounds.

By antifoam compound is meant any compound or mixture thereof which, for example, acts to suppress suds generated by a solution of a detergent composition, especially when the solution is agitated.

Particularly preferred antifoam compounds for use in the present invention are silicone antifoam compounds, which are defined herein as any antifoam compound containing a silicone component. These silicone antifoam compounds typically also contain a silica component. The term "polysiloxane", as used herein, generally includes throughout the industry a variety of relatively high molecular weight polymers containing siloxane and various hydrocarbyl groups. Preferred silicone antifoam compounds are silicones, especially polydimethylsiloxanes with trimethylsilyl end-blocking units.

Other suitable antifoam compounds include monocarboxylic fatty acids and soluble salts thereof. These materials are described in US2954347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof useful as suds suppressors typically have hydrocarbyl chains of 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium, and ammonium and alkoxyammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (such as fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ₁₈ -C ₄₀ ketones (such as stearyl ketone), N-alkylated amino groups Triazines, e.g. as cyanuric chloride with 2 or 3 moles of primary or secondary amines containing 1 to 24 carbon atoms, propylene oxide, bisstearamide and monostearyl dialkali metal (e.g. sodium, potassium, lithium) phosphoric acid Tri to hexaalkylmelamine or di to tetraalkyl diamine aminotriazine formed as a product of salt and phosphate ester.

Preferred suds suppressor systems include:

(a) An antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising a combination of:

(i) polydimethylsiloxane in an amount of 50-99%, preferably 75-95%, by weight of the polysiloxane antifoam compound; and

(ii) silicon dioxide in an amount of 1-50%, preferably 5-25% by weight of the polysiloxane/silica antifoam compound;

Wherein the silicon dioxide/polysiloxane antifoaming compound is added in an amount of 5-50wt%, preferably 10-40wt%;

(b) A dispersant compound, most preferably comprising a polysiloxanediol rake copolymer having a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of 1:0.9-1:1.1, in an amount of 0.5-10 wt%, preferably 1-10 wt%; a particularly preferred polysiloxane diol rake copolymer of this type is DCO544, which is commercially available from DOW Corning under the tradename DCO544.

(c) an inert carrier fluid compound, most preferably containing a _C16 - _C18 ethoxylated alcohol with a degree of ethoxylation of 5-50, preferably 8-15, in an amount of 5-80 wt%, preferably 10-70 wt% ;

A highly preferred granular antifoam system is described in EP-A-0210731 and comprises a polysiloxane antifoam compound and an organic vehicle with a melting point of 50-85°C, wherein the organic vehicle contains glycerol and contains 12-20 carbon A monoester of a fatty acid with a carbon chain of atoms. EP-A-0210721 discloses other preferred granular suds suppressor systems, wherein the organic carrier is a fatty acid or alcohol having a melting point of 45-80° C. with a carbon chain of 12-20 carbon atoms, or a mixture thereof.

Other highly preferred suds suppressor systems contain dimethicone or mixtures of polysiloxanes such as dimethicone, aluminosilicates and polycarboxylic acid polymers such as copolymers of lactic acid and acrylic acid .

polymeric dye transfer inhibitor

The compositions of the present invention may also contain from 0.01 to 10% by weight, preferably from 0.05 to 0.5% by weight, of a polymeric dye transfer inhibiting agent.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof whereby these polymers can for cross-linked polymers.

Fluorescent whitening agent

The compositions of the present invention also optionally contain from about 0.005 to 5% by weight of certain types of hydrophilic optical brighteners, which are known in the art.

polymeric soil release agent

Polymeric soil release agents, hereinafter "SRA", may optionally be used in the compositions of the present invention. The amount of SRA, if used, is generally 0.01-10.0 wt%, typically 0.1-5 wt%, preferably 0.2-3.0 wt%, by weight of the composition.

Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain bonded to them until the end of the wash and rinse cycle, thereby As an immobilizer for hydrophilic fragments. This enables treatment with SRA after contamination has occurred, allowing for easier cleaning in the post-wash step.

Preferred SRAs include oligomeric terephthalates, typically prepared by a process involving at least one transesterification/oligomerization reaction, often using a metal catalyst such as titanium(IV) alcoholate. These esters can be made using other monomers that can add to the ester structure through 1, 2, 3, 4 or more positions, of course without forming a tightly cross-linked overall structure.

Suitable SRAs include an oligoester backbone consisting of terephthaloyl and oxyalkyleneoxy repeat units and a substantially linear ester oligomeric moiety covalently attached to the backbone derived from allyl sulfonated terminal moieties. Sulfonated products of compounds such as those described in US 4,968,451, issued November 6, 1990 to J.J. These ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate in a secondary transesterification/oligomerization step ("DMT") and 1,2-propanediol ("PG"); and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include the non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters of US4711730 issued December 8, 1987 to Gosselink et al. Those produced by transesterification/oligomerization of DMT, PG, and poly(ethylene glycol) ("PEG"). Other examples of SRAs include: partially and fully anionically terminated oligoesters such as ethylene glycol ("EG"), PG, DMT, and 3,6-dioxa-8 in US4721580, Gosselink, Jan. 26, 1988 -Oligomers of sodium hydroxyoctylsulfonate; non-ionic terminated block polyester oligomeric compounds such as DMT, methyl (Me)-blocked PEG and EG in US4702857 issued October 27, 1987 to Gosselink and/or PG, or a combination of DMT, EG and/or PG, Me-blocked PEG and sodium dimethyl-5-sulfoisophthalate; US4877896 issued October 31, 1989 to Maldonado, Gosselink et al Anions in , especially sulfoaroyl, end-capped terephthalates, the latter being SRAs typically used in laundry and fabric conditioning products, an example is derived from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably also ester compositions made with added PEG such as PEG3400.

SRA also includes: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyoxyethylene terephthalate or polyoxypropylene terephthalate, see May 25, 1976 US3959230 issued to Hays on July 8 and US3893929 issued to Basadur on July 8, 1975; cellulose derivatives, such as hydroxyether cellulose polymers available from Dow as METHOCEL; C ₁ -C ₄ alkyl cellulose and C ₄ hydroxy Alkyl celluloses, see US4000093, issued December 28, 1976 to Nicol et al; and methyl cellulose ethers, wherein the average degree of substitution (methyl) per anhydroglucose unit is from about 1.6 to about 2.3, and its 2 The % aqueous solution has a solution viscosity of about 80 to about 120 centipoise measured at 20°C. These materials are available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Other classes of SRAs include: (I) nonionic terephthalates using diisocyanate coupling agents to link polyester structures, see US4201824 to Violland et al. and US4240918 to Lagasse et al; SRA with carboxylate end groups made by adding trimellitic anhydride to convert the terminal hydroxyl groups to trimellitate esters. With the appropriate choice of catalyst, the trimellitic anhydride forms linkages to the polymer ends via the ester of the isolated carboxylic acid of the trimellitic anhydride, rather than via opening of the anhydride linkage. Alternatively, nonionic SRA or anionic SRA can be used as a raw material, as long as they have hydroxyl ends that can be esterified. See US4525524 to Tung et al. Other classes include: (III) Anionic terephthalate-based SRAs of urethane-linked variants, see US4201824 to Violland et al.

other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the present invention include perfumes, speckling agents, colorants or dyes, filler salts, with sodium sulfate being the preferred filler salt.

Also, small amounts (e.g., less than about 20 wt%) of neutralizing agents, buffers, phase regulators, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifying agents, antioxidants, bactericides and Dyes such as those described in US 4,285,841, Barrat et al., issued August 25, 1981 (herein incorporated by reference).

Encapsulated flavors are highly preferred, preferably comprising starch capsules.

In compositions of the present invention, when a dye and/or perfume is sprayed onto another component, it may be preferred that the component is free of sprayed nonionic alkoxylated alcohol surfactant.

composition formation

The compositions of the present invention can be prepared by a number of methods involving mixing the ingredients including: dry blending, compression methods such as agglomeration, extrusion, tabletting, or spray drying of the various compounds contained in detergent components, Or a combination of these techniques whereby the components of the invention can also be made by, for example, molding or spray drying including extrusion and agglomeration.

Compositions of the invention may have a number of physical solid forms including, for example, tablets, flakes, lozenges and bars, and preferably the composition is in the form of granules or tablets.

The compositions according to the invention may also be used in or mixed with, for example, bleach additive compositions comprising chlorine bleach.

The composition preferably has a density of greater than 350 g/l, more preferably greater than 450 g/l or even greater than 570 g/l.

Abbreviations used in the examples

In detergent compositions, the abbreviated components have the following meanings:

LAS: Sodium linear C _11-13 alkylbenzene sulfonate

LAS(I): Contains linear C _11-13 alkylbenzene sulfonate sodium (90%) and

Flakes of Sodium Sulfate and Moisture

LAS(II): Potassium linear C _11-13 alkylbenzene sulfonate

MES: α-sulfo C ₁₈ fatty acid methyl ester

TAS : Sodium Tallow Alkyl Sulfate

CxyAS: sodium C _1x -C _1y alkyl sulfate

C46SAS: Sodium C ₁₄ -C ₁₆ secondary (2,3) alkyl sulfate

CxyEzS: C _1x -C _1y alkyl condensed with z moles of ethylene oxide

Sodium Sulfate

CxyEz: C _1x condensed with average z moles of ethylene oxide −

C _1y is mainly a linear primary alcohol

QAS: R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), where R ₂ =C ₁₂ -C ₁₄

QAS1: R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), where R ₂ =C ₈ -C ₁₁

SADS: C ₁₄ -C ₂₂ of the formula 2-(R).C ₄ H ₇ .-1,4-(SO ₄ -) ₂

Sodium alkyl pyrosulfate, where R=C ₁₀ -C ₁₈

SADE2S : Formula for condensation with z moles of ethylene oxide

C ₁₄ -C ₂₂ alkyl of _2- (R).C ₄ H ₇ .-1,4-(SO ₄ -) 2

Sodium sulfate, where R=C ₁₀ -C ₁₈

APA : C ₈ -C ₁₀ Amidopropyl Dimethylamine

Soap: Derived from an 80/20 blend of tallow and coconut fatty acids

Sodium linear alkyl carboxylate

STS       : Sodium Toluene Sulfonate

CFAA : C ₁₂ -C ₁₄ (cocoa) alkyl N-methyl glucamide

TFAA: C ₁₆ -C ₁₈ Alkyl N-methyl Glucamide

TPKFA: C ₁₆ -C ₁₈ Topped Full Fraction Fatty Acids

STPP : Sodium tripolyphosphate anhydrous

TSPP : Tetrasodium pyrophosphate

Zeolite A: Aluminum silicon hydrate of the formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O

Sodium phosphate, the main particle size range is 0.1-10 microns (in

          Anhydrous weight scale)

NaSKS-6(I): crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅ , weight average

A particle size of 18 microns, with at least 90 wt% of the particle size low

At 65.6 microns.

NaSKS- : crystalline phyllosilicate of formula δ-Na ₂ Si ₂ O ₅ , weight average

6(II) A particle size of 18 microns, with at least 90 wt% of the particle size lower

At 42.1 microns.

Citric acid : Anhydrous citric acid

Borates : Sodium borate

Carbonate : Anhydrous sodium carbonate, particle size distribution between 200 microns and

Between 900 microns

Bicarbonate: Anhydrous sodium bicarbonate, particle size distribution in 400 microns

Between and 1200 microns

Silicate: Amorphous sodium silicate (SiO ₂ :Na ₂ O=2.0:1)

Sulphate : Sodium Sulfate Anhydrous

Magnesium Sulfate : Anhydrous Magnesium Sulfate

Citrate: Trisodium citrate dihydrate, 86.4% active,

Particle size distribution between 425 microns and 850 microns

MA/AA : 1:4 maleic acid/acrylic acid copolymer, average score

Subquantity is about 70000

MA/AA(1) : 4:6 maleic acid/acrylic acid copolymer, average score

Subquantity is about 10000

AA : Sodium polyacrylate polymer with an average molecular weight of

4500

CMC : Sodium Carboxymethyl Cellulose

Cellulose ether : Methyl cellulose ether, the degree of polymerization is 650, available from

Shin Etsu Chemicals acquired

Proteases : Proteolytic enzymes with 3.3 wt% active enzymes, composed of

NOVO Industrial A/S sells it under the trade name Savinase

Protease I: Proteolytic enzyme with 4wt% active enzyme, such as

as described in WO95/10591 by Genencor Int.

Sales by Inc.

Alcalase : Proteolytic enzyme, with 5.3wt% active enzyme, composed of

NOVO Industrial A/S Sales

Cellulase: cellulolytic enzyme with 0.23 wt% active enzyme,

by NOVO Industrial A/S under the trade name Carezyme

Sale

Amylase : Amylolytic enzyme with 1.6 wt% active enzyme, composed of

NOVO Industrial A/S trade name Termamyl

120T sales

Amylase II : amylolytic enzyme, as described in PCT/US9703635

public

Lipase: lipohydrolase, with 2.0 wt% active enzyme, composed of

NOVO Industrial A/S sells it under the trade name Lipolase

Lipase (1) : lipohydrolase, with 2.0 wt% active enzyme, composed of

NOVO Industrial A/S trade name Lipolase

Sales of Ultra

Endoenzyme: Endoglucanase, with 1.5 wt% active enzyme, composed of

NOVO Industrial A/S Sales

PB4 : Sodium perborate tetrahydrate, standard formula

NaBO ₂ .3H ₂ OH ₂ O ₂

PB1 : Anhydrous sodium perborate bleach, standard formula

NaBO ₂ .H ₂ O ₂

Percarbonate: sodium percarbonate, nominal formula 2Na ₂ CO ₃ .3H ₂ O ₂

DOBS : Sodium Decanoyloxybenzene Sulfonate

DPDA : Peroxydodecanedioic acid

NOBS : Sodium Nonanoyloxybenzene Sulfonate

NACA-OBS : (6-Nonanoylaminocaproyl)oxybenzenesulfonate

LOBS : Sodium Dodecanoyloxybenzene Sulfonate

DOBS : Sodium Nonanoyloxybenzene Sulfonate

DOBA : Nonanoyloxybenzenesulfonic acid

TAED ： Tetraacetylethylenediamine

DTPA : Diethylenetriaminepentaacetic acid

DTPMP : Ethylenetriaminepenta(methylene phosphonate), composed of

Monsanto sells under the trade name Dequest 2060

for sale

EDDS : Ethylenediamine-N,N'-disuccinic acid, in the form of its sodium salt

The (S, S) isomer of

Photoactivated bleaching: encapsulated in soluble polymers or by soluble

Sulfonated zinc phthalocyanine (dye) or sulfonated

                                    

Brightener 1 : 4,4'-bis(2-sulfostyrene)biphenyl disodium

Brightener 2 : 4,4'-bis(4-anilino-6-morpholinyl-1,3,5-

        Triazin-2-yl)amino)stilbene-2:2’-disulfonic acid di

Sodium

HEDP : 1,1-Hydroxyethylenediphosphonic acid

PEGx : Polyethylene glycol with a molecular weight of x (typically 4000)

PEO: Polyoxyethylene, with an average molecular weight of 50,000

TEPAE ： Tetraethylenepentamine ethoxylate

PVI : Polyvinylimidazole, with an average molecular weight of 20,000

PVP : Polyvinylpyrrolidone polymer, average molecular weight

is 60000

PVNO : Polyvinylpyridine N-oxide polymer, average

The molecular weight is 50000

PVPVI : Co-polymer of polyvinylpyrrolidone and vinylimidazole

Polymer with an average molecular weight of 20,000

QEA: Di((C ₂ H ₅ O)(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -

(CH ₃ ) two ((C ₂ H ₅ O)-(C ₂ H ₄ O)) _n , where

n=20-30

SRP 1 : Anion-terminated polyester

SRP 2 : Diethoxylated poly(1,2propyl terephthalate)

                                                                                             

PEI : Polyethyleneimine

(Polyethyleneimine), average molecular weight

is 1800 with an average degree of ethoxylation of 7 per nitrogen

Ethyleneoxy residues

Silicone Disinfectant: Dimethicone foam control agent with silicone

Foaming agent Alkane-oxyalkylene copolymer as a dispersant, the foam

The ratio of the foam control agent to the dispersant is 10:1-

100:1

Sunscreen: Water-based monostyrene latex blend by BASF

Aktiengesellschaft trade name

Lytron 621 Sales

Waxes: Paraffin

Example 1 A B C D E F G h I blown powder LAS 5.0 8.0 3.0 5.0 5.0 10.0 - - - TAS - 1.0 - - - - MBAS - - 5.0 5.0 - - - C ₄₅ AS - - 1.0 2.0 2.0 - - - C ₄₅ AE ₃ S - - 1.0 - - - QAS 1.0 1.0 - - - DTPA, HEDP and/or EDDS 0.3 0.3 0.5 0.3 - - - MgSO4 0.5 0.5 0.1 - - - - Sodium citrate - - - 3.0 5.0 - - - Sodium carbonate 10.0 7.0 15.0 10.0 - - - sodium sulfate 5.0 5.0 - - 5.0 3.0 - - - Sodium silicate 1.6R - - - - 2.0 - - - Zeolite A 16.0 18.0 20.0 - - - - - - SKS-6 - - - 3.0 5.0 - - - - MA/AA or AA 1.0 2.0 11.0 - - 2.0 - - - PEG4000 - 2.0 - 1.0 - 1.0 - - - QEA 1.0 - - - 1.0 - - - - Whitening agent 0.05 0.05 0.05 - 0.05 - - - - Silicone oil 0.01 0.01 0.01 - - 0.01 - - - Agglomerates LAS - - - - - 2.0 - MBAS - - - - 2.0 - 1.0

C24AE ₃ - - - - - 1.0 0.5 carbonate - - - 1.0 1.0 1.0 - Sodium citrate - - - - - - 5.0 CFAA - 2.0 - - 2.0 QAS - - - 1.0 - 1.0 1.0 QEA - - - 2.0 2.0 1.0 - SRP - - - 1.0 1.0 0.2 - Zeolite A - - - 10.0 26.0 15.0 16.0 Sodium silicate - - - - - - - PEG - - - - - - 4.0 - - Agglomerates SKS-6 6.0 8.0 - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 Dry Add Granular Components Maleic acid/carbonate/bicarbonate 8.0 10.0 10.0 4.0 - 8.0 2.0 2.0 4.0 (40:20:40) QEA - - - 0.2 0.5 - - - - NACAOBS 3.0 - - 1.5 - - - 2.5 - NOBS - 3.0 3.0 - - - - - 5.0 TAED 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS(I) 10.0 10.0 10.0 - - - 12.0 8.0 -

spray on brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 - Dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - Spices - - - 0.8 - 0.5 - 0.5 - dry plus Citrate - - 20.0 4.0 - 5.0 15.0 - 5.0 percarbonate 15.0 3.0 6.0 10.0 - - - 18.0 5.0 Perborate - - - - 6.0 18.0 - - - photobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, amylase, protease, lipase) 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 Zeolite A - - - 10.0 10.0 - - - - Carbonate 0.0 10.0 - - - 5.0 8.0 10.0 5.0 Spices (encapsulated) 0.6 0.5 0.5 - 0.3 0.5 0.2 0.1 0.6 Antifoam 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - citric acid - - - 6.0 6.0 - - - 5.0 Dyed carbonate (blue, green) 0.5 0.5 1.0 2.0 - 0.5 0.5 0.5 1.0 SKS-6 - - - 4.0 - - - 6.0 - Fill to 100%

Example 2

Following is the detergent formula according to the present invention: J K L m blown powder Zeolite A 12.0 20.0 - - sodium sulfate - 5.0 2.0 - LAS - 10.0 3.0 - C45AS - 4.0 4.0 - QAS - - 1.5 - DTPA/HEDP/EDDS 0.4 0.4 0.4 - CMC 0.4 0.4 0.4 - carbonate - - 3.0 - AA or MA/AA 4.0 2.0 10.0 - Agglomerates QAS 1.0 - - - LAS 1.0 - 2.0 10.0 TAS - - - 1.0 Silicate 1.0 - - 0.3 Zeolite A 8.0 - 8.0 3.0 carbonate 8.0 - 4.0 3.0 Agglomerates NaSKS-6 15.0 12.0 - 10.0 LAS 8.0 13.0 - 8.0 AS 5.0 - - spray on spices 0.3 0.3 0.3 0.5

Whitening agent 0.01 0.01 0.01 0.01 C25E5 2.0 - 1.0 -   Dry Additives LAS(I) - - 7.0 - QEA 1.0 0.5 0.5 0.5 Citrate - - 10.0 - Bicarbonates - 3.0 - carbonate 8.0 15.0 10.0 - NAC OBS 4.0 - - - TAED 2.0 - 0.3 5.0 NOBS - 2.0 3.0 - PC/PB1 14.0 3.0 3.0 18.0 PEG - - 0.9 0.5 Soap - 0.5 - - Malic acid 7.0 - - - Zeolite A 2.0 - - -   Polyoxyethylene with a MW of 5,000,000 - - - - Citric acid - - - 5.0 Protease 1.0 0.5 0.3 0.5 Lipase - 0.4 - - Amylase 0.6 0.6 0.6 Zeolite A - - 16.0 10.0 Cellulase 0.6 0.2 - 0.3 SKS-6 - - 10.0 - SRP 0.1 0.1 0.1 0.1 CMC - 0.3 - 0.5 PVP - - 0.1 0.2   Polysiloxane defoamer 0.5 1.5 1.0 0.3

sodium sulfate 0.0 3.0 0.0 - Balance (moisture and impurities) 100.0 100.0 100.0 Density (g/L) 800 600 700 850

Example 3

Following is the detergent formula according to the present invention: N o P R Agglomerates QAS 2.0 - 2.0 - MES - 2.0 - - LAS(II) 6.0 - - - C45AS 6.0 4.0 2.0 - MBAS16.5, 1.9 4.0 - - - Zeolite A - 6.0 8.0 8.0 carbonate 4.0 8.0 - 8.0 MA/AA 4.0 2.0 2.0 6.0 CMC 0.5 0.5 1.0 0.5 DTPMP 0.4 0.4 - 0.5 spray on C25E3 1.0 1.0 - - spices 0.5 0.5 0.5 0.5 Agglomerates SKS-6 7.0 15.0 15.0 10.0 LAS 3.0 9.0 15.0 10.0 Zeolite 15.0 - - - C45AS - 3.0 - - dry addition LAS(I) - - - 15.0 EDDS/HEDP 0.5 0.3 0.5 0.8 Zeolite A 3.0 12.0 5.0 3.0 NaSKS6 - - - 11.0 Citrate - 1.0 - - citric acid 2.0 - 2.0 4.0 NAC OBS 4.1 - 5.0 4.0 TAED 0.8 2.0 - 2.0 Percarbonate 20.0 20.0 15.0 17.0 SRP 1 0.3 0.3 - 0.3 protease 1.4 1.4 1.0 0.5 Lipase 0.4 0.4 0.3 - cellulase 0.6 0.6 0.5 0.5 Amylase 0.6 0.6 - 0.3 QEA 1.0 - 1.0 1.0 Polysiloxane defoamer 1.0 0.5 0.5 1.5 Brightener 1 0.2 0.2 - 6.2 brightener 0.2 - 0.2 - Density(g/L) 850 850 800 775

Claims (14)

1. detergent composition, contain aluminosilicate washing assistant and anion surfactant and comprise n kind component (i), n is at least 2, wherein the content of aluminosilicate washing assistant in all described components is at least 5% of composition weight, and the content of anion surfactant in all described components is at least 5% of composition weight, it is characterized in that described composition comprises the component that component that at least a spray-drying process makes and at least a agglomeration technique are made, and the mixedness of anion surfactant and aluminosilicate washing assistant (M) is 0-0.7, and M is

∑ ⁿ _i＝1√(σ ₁.ζ _i)

σ is the mark of the anion surfactant of contained composition in the component (i);

ζ is the mark of the aluminosilicate of contained composition in the component (i).

2. detergent composition as claimed in claim 1, wherein M is 0-0.65.

3. detergent composition as claimed in claim 2, wherein M is 0-0.5.

4. detergent composition as claimed in claim 3, wherein M is 0-0.45.

5. detergent composition as claimed in claim 1, wherein said component are weight average particle diameter greater than 150 microns particle.

6. detergent composition as claimed in claim 5, wherein said component are that weight average particle diameter is greater than 350 microns.

7. detergent composition as claimed in claim 1, wherein anion surfactant comprises alkyl sulfonate surfactants or alkyl sulfate surfactant, or its mixture.

8. detergent composition as claimed in claim 7, wherein anion surfactant comprises alkyl benzene sulfonate surfactant.

9. detergent composition as claimed in claim 1 contains the aluminosilicate washing assistant of at least 10 weight %, and wherein the described aluminosilicate of part is not included in the described component.

10. detergent composition as claimed in claim 9, wherein the described silicate of part mixes with described component.

11. detergent composition as claimed in claim 1, wherein said component are not spray the component that goes up nonionic alcohol alcoxylates tensio-active agent.

12. wherein there is the foaming system in composition as claimed in claim 1.

13. composition as claimed in claim 1 contains hydrogen peroxide cource and bleach-activating agent.

14. composition as claimed in claim 1 is particle form or tablet form.